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Azamacrocyclic stabilisation of the halogenocations MX3(+) where M=Ge or Sn and X=Cl or Br. Synthesis and molecular structures of [GeCl3(L-1)](+)(2)[H3O]Cl-+(3)-.MeCN, [SnCl3(L-1)](+)(2)[SnCl6](2-).4MeCN, [GeBr3(L-2)](+)(2)[MeNH3]Br-+(3)-.MeCN and [SnBr3(L-2)](+)(2)[SnBr6](2-) where L-1=1,4,7-trimethyl-1,4,7-triazacyclononane and L-2=1,3,5-trimethyl-1,3,5-triazacyclohexane
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UNSPECIFIED (1998) Azamacrocyclic stabilisation of the halogenocations MX3(+) where M=Ge or Sn and X=Cl or Br. Synthesis and molecular structures of [GeCl3(L-1)](+)(2)[H3O]Cl-+(3)-.MeCN, [SnCl3(L-1)](+)(2)[SnCl6](2-).4MeCN, [GeBr3(L-2)](+)(2)[MeNH3]Br-+(3)-.MeCN and [SnBr3(L-2)](+)(2)[SnBr6](2-) where L-1=1,4,7-trimethyl-1,4,7-triazacyclononane and L-2=1,3,5-trimethyl-1,3,5-triazacyclohexane. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS (15). pp. 2573-2576. ISSN 0300-9246.
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Abstract
Treatment (1 : 1 in acetonitrile) of the reaction systems MCl4-1,4,7-trimethyl-1,4,7-triazacyclononane (L-1) and MBr4-1,3,5-trimethyl-1,3,5-triazacyclohexane (L-2), where M-IV = Ge or Sn, provided ionic compounds featuring the trihalogenocationic species [MX3(L-n)](+) rather than direct adduct formation [MX4(L-n)]. Crystal structure determinations (X-ray diffraction) confirmed an ionic formulation for each of the four products isolated, viz. [GeCl3(L-1)](+)(2)[H3O]Cl-+(3)-. MeCN 1, [SnCl3(L-1)](+)(2)[SnCl6](2-). 4MeCN 2, [GeBr3(L-2)](+)(2)[MeNH3]Br-+(3)-. MeCN 3, and [SnBr3(L-2)](+)(2)[SnBr6](2-) 4. Ligand attachment to M-IV, both for L-1 and L-2, is terdentate N-donor (eta(3)) throughout and the resulting six-co-ordinate cations [MX3(L-n)](+) show the anticipatedfac-octahedral metal geometry. Individual M-N bond distances within each cation are the same, viz. mean values 2.113(2) 1, 2.244(8) 2, 2.142(7) 3, 2.311(6) Angstrom 4, reflecting a uniform central location of the MX3+ unit over the ring cavity. The 'cone angle' N-ring-M-N-ring values (mean) for compounds 3 64.3(3) and 4 59.7(2)degrees involving L-1 are conspicuously smaller, ca. 20 degrees, than those for compounds 1 82.90(8) and 2 79.1(3)degrees involving L-2 as a reflection of the insistent steric demands of the more compact six-membered triazacyclohexane ligand.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Journal or Publication Title: | JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | ||||
Publisher: | ROYAL SOC CHEMISTRY | ||||
ISSN: | 0300-9246 | ||||
Official Date: | 7 August 1998 | ||||
Dates: |
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Number: | 15 | ||||
Number of Pages: | 4 | ||||
Page Range: | pp. 2573-2576 | ||||
Publication Status: | Published |
Data sourced from Thomson Reuters' Web of Knowledge
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